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Ca K‑Edge XAS as a Probe of Calcium Centers in Complex Systems

Martin-Diaconescu, Vlad and Gennari, Marcello and Gerey, Bertrand and Tsui, Emily and Kanady, Jacob and Tran, Rosalie and Pécaut, Jacques and Maganas, Dimitrios and Krewald, Vera and Gouré, Eric and Duboc, Carole and Yano, Junko and Agapie, Theodor and Collomb, Marie-Noelle and DeBeer, Serena (2014) Ca K‑Edge XAS as a Probe of Calcium Centers in Complex Systems. Inorganic Chemistry, 54 (4). pp. 1283-1292. ISSN 0020-1669. PMCID PMC4331723. doi:10.1021/ic501991e.

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Herein, Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers. The spectra for six, seven, and eight coordinate inorganic and molecular calcium complexes were analyzed and determined to be primarily influenced by the coordination environment and site symmetry at the calcium center. The experimental results are closely correlated to time-dependent density functional theory (TD-DFT) calculations of the XAS spectra. The applicability of this methodology to complex systems was investigated using structural mimics of the oxygen-evolving complex (OEC) of PSII. It was found that Ca K-edge XAS is a sensitive probe for structural changes occurring in the cubane heterometallic cluster due to Mn oxidation. Future applications to the OEC are discussed.

Item Type:Article
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URLURL TypeDescription Information CentralArticle
Tsui, Emily0000-0001-6419-3954
Yano, Junko0000-0001-6308-9071
Agapie, Theodor0000-0002-9692-7614
DeBeer, Serena0000-0002-5196-3400
Additional Information:© 2014 American Chemical Society. ACS Editors' Choice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: August 15, 2014. Published: December 10, 2014. V.M.-D., D.M., V.K., and S.D. acknowledge the Max Planck Society for funding. S.D. acknowledges a Sloan Fellowship. B.G. thanks the “Université Joseph Fourier of Grenoble” for his Ph.D. grant. The Authors acknowledge support from ICMG FR 2067, COST CM1202 program (PERSPECT H2O), LABEX ARCANE (ANR-11-LABX-0003-01), the French National Research Agency (ANR-09-JCJC-0087 (MANGACOM), and ANR-13-BS07-0015-01 (MnCaOEC)) for financial support including M.G.’s and E.G.’s fellowships. We are grateful to the NIH (R01 GM102687A to T.A.); Dreyfus, Sloan, and Cottrell fellowships (T.A.); the NSF (GRFP to J.K. and E.T.); and Sandia National Laboratory (fellowship to E.T.) for funding. A portion of the XAS work was supported by NIH Grant F32GM100595 (R.T.), and by the Director of the Office of Basic Energy Science (OBES), Division of Chemical Sciences, Geosciences, and Biosciences, DOE, under contract DE-AC02-05CH11231 (J.Y). Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract No.DE-AC02-76SF00515. Parts of this research were carried out at the light source DORIS at DESY, a member of the Helmholtz Association (HGF). We would like to thank Dr. Edmund Welter for assistance in using beamline A.1.
Funding AgencyGrant Number
Max Planck SocietyUNSPECIFIED
Alfred P. Sloan FoundationUNSPECIFIED
Université Joseph Fourier of GrenobleUNSPECIFIED
Centre National de la Recherche Scientifique (CNRS)PERSPECT H2O
Agence Nationale pour la Recherche (ANR)ANR-11-LABX-0003-01
Agence Nationale pour la Recherche (ANR)ANR-09-JCJC-0087 (MANGACOM)
Agence Nationale pour la Recherche (ANR)ANR-13-BS07-0015-01 (MnCaOEC)
NIHR01 GM102687A
Camille and Henry Dreyfus FoundationUNSPECIFIED
Sandia National LaboratoryUNSPECIFIED
NIH Postdoctoral FellowshipF32GM100595
Department of Energy (DOE)DE-AC02-05CH11231
Department of Energy (DOE)DE-AC02-76SF00515
Cottrell Scholar of Research CorporationUNSPECIFIED
Issue or Number:4
PubMed Central ID:PMC4331723
Record Number:CaltechAUTHORS:20150324-125850453
Persistent URL:
Official Citation:Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems Vlad Martin-Diaconescu, Marcello Gennari, Bertrand Gerey, Emily Tsui, Jacob Kanady, Rosalie Tran, Jacques Pécaut, Dimitrios Maganas, Vera Krewald, Eric Gouré, Carole Duboc, Junko Yano, Theodor Agapie, Marie-Noelle Collomb, and Serena DeBeer Inorganic Chemistry 2015 54 (4), 1283-1292 DOI: 10.1021/ic501991e
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:56032
Deposited By: Ruth Sustaita
Deposited On:24 Mar 2015 22:31
Last Modified:10 Nov 2021 20:53

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